Substituted bicycloheptandione derivatives

ABSTRACT

This invention relates to substituted bicycloheptadione derivatives with high herbicidal activity which are represented by general formula (I) ##STR1## (where R 1  is a lower alkyl group, a phenyl group which may be substituted, an aralkyl group which may be substituted, or a heterocyclic group which may be substituted; 
     R 2  is, same or different, a halogen, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkyl group, an alkoxyalkyl group, or an alkoxylcarbonyl group, and n is 0 to 4; 
     R 3  and R 4  are, same or different, hydrogen or a lower alkyl group).

DESCRIPTION

1. Technical Field:

This invention relates to new substituted bicycloheptandione derivatives, their preparation methods and herbicides containing the said derivatives as effective components.

2. Background Art:

In many cases of agricultural or horticultural cultivation, a lot of kinds and amount of herbicides have come to be used for the weed control in order to save the labors consuming for removing weeds in the fields, however, in some occasion, phytotoxicity of herbicides may injure crops, or herbicides remaining in the field may cause environmental pollution.

Consequently, chemicals possessing the excellent efficacy and the higher safety to mammal have been awaited to be developed.

Known patents disclosing compounds analogous to the compounds of this invention include EP-137963, EP-135191, EP-186118, EP-186119, EP-186120, Japanese open patent No. Sho 62-123145, EP-278907, EP-268795 and EP-264737.

The compounds of this invention are included in the claims of DE 3902818 (Corresponding to GB 2215333 and Japanese open patent No. Hei 2-1422). There are no descriptions on the compounds of this invention in the Description.

An object of this invention is to provide herbicides which are synthesized advantageously in an industrial scale, have certain efficacy at a lower dosage, are very safe and have well selectivity to crops.

DISCLOSURE OF INVENTION

This invention is substituted bicycloheptandione derivatives having the formula (I) ##STR2## (where R¹ is a lower alkyl group, a phenyl group which may be substituted, an aralkyl group which may be substituted, or a heterocyclic group which may be substituted;

R² is, same or different, a halogen, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkyl group, an alkoxyalkyl group, or an alkoxycarbonyl group, and n is 0 to 4;

R³ and R⁴ are, same or different, hydrogen or a lower alkyl group), or their salts.

The said substituents of the phenyl, aralkyl and heterocyclic groups of R¹ are, same or different, halogen, hydroxy, nitro, cyano, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, haloalkoxy, haloalkenyloxy, alkylthio, alkenylthio, alkynylthio, haloalkylthio, haloalkenylthio, monoalkylamino, dialkylamino, alkoxyalkylthio, alkylthioalkylthio, alkoxycarbonyl, alkylcarbonylalkoxy, alkylcarbonyl, alkoxyamino, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, alkoxyalkylsulfonyl, alkylthioalkylsulfonyl, alkylsulfonylalkylsulfonyl, haloalkylsulfonyl, alkoxycarbonylalkylthio, alkoxycarbonylalkylsulfinyl alkoxycarbonylalkylsulfonyl, alkylamido, and aralkyloxy a phenyl group which may be substituted, an aralkyl group which may be substituted, a heterocyclic group which may be substituted, and an alkyl group substituted by a heterocyclic group which may be substituted.

The said heterocyclic group includes groups of pyridyl, pyrimidyl, thienyl, furyl, pyrazolyl, pyrrolyl, imidazolyl, pyridazinyl, pyrazinyl, indolyl and others.

The compounds of this invention exhibit high herbicidal activity under upland conditions by either method of soil treatment or plat foliage treatment. It is very efficacious against various kinds of upland weeds such as crabgrass, rice flatsedge velvetheaf and redroot pigweed, in a treatment of spraying it directly on the foliage of plant in particular. Same of these compounds have selectivity to crops such as wheat and soy beans.

Some of these compounds show plant growth retardent activity on crops, ornamental pot plants and fruit trees.

Some compounds also exhibit high selectivity on rice plant and high herbicidal activity against barnyard grass, smallflower unbrellaplant, arrowhead and Japanese bulrush, etc.

In addition to the above, the compounds of this invention can be applied for weed control to such places as orchards, lawn, railroad sides and vacant lots, etc.

BEST MODE FOR CARRYING OUT THE INVENTION

The compounds of this invention are prepared by the following methods.

Preparation Method (a) ##STR3## (where R¹, R², R³, R⁴, and n are as defined above, and Q is a leaving group).

In the process, Compound (I) is obtained in a way that Compound (II) is reacted in a solvent in the presence of 2 moles or an excessive amount of base at a temperature from -20° C. to the boiling point of the solvent used, preferably 0° C. to 50° C., for 30 minutes to several 10 hours.

The leaving group of Q includes halogen, alkylsulfonate and phenylsulfonate. Bases used include alkali metal hydroxides such as KOH and NaOH, hydroxides of alkaline earth metals, tri (C₁ -C₆ alkyl) amine, pyridine, DBU, t-BuOK, Triton B, sodium carbonate, sodium phosphate or the like. Solvents used include water, alcohol, methylene chloride, benzene, toluene, ethyl acetate, dimethylformamide, THF, dimethoxyethane, acetonitrile or the like.

Preparation Method (b)

Mono-substituted compounds, among the compounds of this invention, except those of which an alkoxycarbonyl group is at the 5 position of the bicyclo ring, may be prepared according to the following reaction. ##STR4## (where r is an alkyl group).

If these compounds have different substituents at the 5 positions such as (I)' or one substituent at the 5 position such as (I)", stereoisomers exist with respect to the cyclopropane ring.

When [I]" is directly produced according to the above-described Preparation Method (a), the trans form is usually produced. In the preparation method, it is possible to separate cis and trans forms at the stage of [I]'. An appropriate selection of the methods allows to prepare the trans or cis form of [I]".

The material compound and the compound [I] of this invention have optical isomers, and a large number of tautomers can exist in the form of ##STR5## (where R¹, R², R³, R⁴ and n are as defined above). The compounds of such forms are all included in this invention.

If Compound [I] contains a free hydroxyl group when prepared by the above-described method, salts of the said compound, salts allowed particularly agriculturally and horticulturally, enamines and their analogues, acrylate, sulfonate, carbamate or ether can be derived from the said compound.

Appropriate salts allowed agriculturally and horticulturally include salts of sodium, potassium, calcium, ammonium or the like.

Examples of ammonium salts are salts with ion represented by formula N⁺ R^(a) R^(b) R^(c) R^(d) (where R^(a), R^(b), R^(c) and R^(d) are respectively selected from hydrogen and C₁₋₁₀ alkyl groups substituted by, for instance, hydroxy group for some cases). If any of R^(a), R^(b), R^(c) and R^(d) are substituted alkyl groups in some cases, it is desirable that the group has 1 to 4 carbon atoms.

Appropriate enamines and their analogues are compounds of which their OH groups are respectively converted to a group represented by formula --NR^(e) R^(f) (where R^(e) is for instance an alkyl or aryl group having 1 to 6 carbon atoms and which may be substituted in some cases, or for instance a phenyl group, and

R^(f) is hydrogen, or for instance an alkyl or aryl group having 1 to 6 carbon atoms and which may be substituted in some cases, or for instance a phenyl group), halogen or SR^(g). (Where R^(g) is the same group as the above-described group R^(e))

Appropriate acrylate or ether derivatives are compounds of which their OH groups are respectively converted to a group represented by formula --OCOR^(h) or --OR^(h) (where R^(h) is the same group as the above-described group R^(e)).

Appropriate carbamate derivatives are compounds of which their OH groups are converted to a group represented by formula --OC(O)NR^(i) R^(j) (where R^(i) and R^(j) are respectively hydrogen or the same as the above-described R^(e)).

These derivatives can be prepared by usual methods.

The structure of the compounds of this invention are determined by such means as IR, NMR and MS.

This invention is further described in detail by reference to the following examples.

EXAMPLE 1

3-(2-nitro-4-chlorobenzoyl) bicyclo[4,1,0]heptane-2,4-dione (Compound I-97) ##STR6##

0.5 g (1.44 mmol) of 5-mesyloxymethyl-2-(2-nitro-4-chlorobenzoyl)cyclohexane-1,3-dione was dissolved in 15 ml of ethanol, to which 2 ml of aqueous solution of sodium hydroxide (sodium hydroxide: 0.17 g, 4.31 mmol) was added with stirring at room temperature and resulting mixtures stirred at room temperature for another 2 hours. After the reactin was completed, the solvent was distilled. To the obtained residue were added 50 ml of ethyl acetate and 10 ml of water to dissolve it. Dilute hydrochloric acid was added until the aqueous layer became acidic. The organic layer was washed with saturated salt water and dried with magnesium sulfate. The solvent was distilled. The obtained residue was purified with silica gel column chromatography (eluate:chloroform) to give 0.38 g (yield: 86%) of the intended product of light yellow crystal. m.p. 132°-134° C.

EXAMPLE 2

3-(2-chloro-4-methylsulfonyl-3-methoxybenzoyl)-cis-5-methyl-cis-bicyclo[4,1,0]heptane-2,4-dione (Compound I-195) ##STR7##

1.19 g (2.6 mmol) of 3-(2-chloro-4-methanesulfonyl-3-methoxybenzoyl)-trans-5-ethoxycarbonyl-cis-5-methyl-cis-bicyclo[4,1,0]heptane-2,4-dione was dissolved in 7.8 ml (7.8 mmol) of 1N-NaOH while cooling with ice water, then reacted at room temperature for 4 hours. After the reaction was completed, 20 ml of ice water and 20 ml of ethyl acetate were added, neutralized with 1N-HCl while cooling with ice water, and decarboxylated. The organic layer was washed with water and then with saturated salt water, and dried with MgSO₄. The solvent was distilled. The residue was purified with column chromatography (benzene:ethyl acetate=5:1) to give 0.29 g of the intended product of white crystal. m.p. 132°-135° C. The obtained cis form and the trans form synthesized in the same manner as that used in Example 1 were characterized with NMR.

Representative examples of the compounds of this invention, including those obtained in the above examples, are shown in Tables 1 to 3.

Rx, Ry and Rz are the following substituents respectively in the tables. The trans and cis in the column of physical property are steric configurations of the substituent at the 5 position of the bicyclo ring and the cyclopropane ring. ##STR8##

                                      TABLE 1                                      __________________________________________________________________________     Structural Formula                                                             No.                                                                               (R2)n     R3 R4 Xm                Physical Properties                       __________________________________________________________________________     I-1                                                                               --(n = 0) H  H  H                                                           I-2                                                                               --        H  H  2-Br-3-OCH3-4-OCH3                                          I-3                                                                               --        H  H  2-C2H5-4-SO2CH3                                             I-4                                                                               --        H  H  2-CF3                                                       I-5                                                                               --        H  H  2-CF3-4-CF3                                                 I-6                                                                               --        H  H  2-CF3-4-Cl                                                  I-7                                                                               --        H  H  2-CF3-4-SO2CH3                                              I-8                                                                               --        H  H  2-CH3                                                       I-9                                                                               --        H  H  2-CH3-3-CH2-CH3-4-SO2CH3                                    I-10                                                                              5-CH3     H  H  2-CH3-3-CH2OCH3-4-SO2CH3                                                                         mp 128-130(trans)                         I-11                                                                              1-CH3     H  H  2-CH3-3-CH2OCH3-4-SO2CH3                                    I-12                                                                              5,5-(CH3)2                                                                               H  H  2-CH3-3-CH2OCH3-4-SO2CH3                                    I-13                                                                              1,5,5-(CH3)3                                                                             H  H  2-CH3-3-CH2OCH3-4-SO2CH3                                    I-14                                                                              --(n = 0) CH3                                                                               CH3                                                                               2-CH3-3-CH2OCH3-4-SO2CH3                                    I-15                                                                              --        H  H  2-CH3-3-CH2SCH3-4-SO2CH3                                    I-16                                                                              --        H  H  2-CH3-3-CH2SO2CH3-4-SO2CH3                                  I-17                                                                              --        H  H  2-CH3-3-CH3-4-CF3                                           I-18                                                                              --        H  H  2-CH3-3-CH3-4-Cl                                            I-19                                                                              --        H  H  2-CH3-3-CH3-4-SO2C3H7 (i)                                   I-20                                                                              --        H  H  2-CH3-3-CH3-4-SO2CH3                                                                             powder                                    I-21                                                                              5-CH3     H  H  2-CH3-3-CH3-4-SO2CH3                                                                             mp 178-180(trans)                         I-22                                                                              1-CH3     H  H  2-CH3-3-CH3-4-SO2CH3                                        I-23                                                                              5,5-(CH3)2                                                                               H  H  2-CH3-3-CH3-4-SO2CH3                                        I-24                                                                              1,5,5-(CH3)3                                                                             H  H  2-CH3-3-CH3-4-SO2CH3                                        I-25                                                                              --(n = 0) H  H  2-CH3-3-CH3-4-SO2CH3                                        I-26                                                                              --        H  H  2-CH3-3-Cl-4-Cl                                             I-27                                                                              --        H  H  2-CH3-3-Cl-4-OCH3                                           I-28                                                                              --        H  H  2-CH3-3-Cl-4-SCH3                                           I-29                                                                              --        H  H  2-CH3-3-Cl-4-SO2C3H7(i)                                     I-30                                                                              --        H  H  2-CH3-3-Cl-4-SO2CH3                                         I-31                                                                              --(n = 0) H  H  2-CH3-3-Cl-4-SOCH3                                          I-32                                                                              --        H  H  2-CH3-4-CN                                                  I-33                                                                              --        H  H  2-CH3-4-SCH2OCH3                                            I-34                                                                              --        H  H  2-CH3-4-SO2C3H7 (i)                                         I-35                                                                              --        H  H  2-CH3-4-SO2CH3    mp 151-3                                  I-36                                                                              5-CH3     H  H  2-CH3-4-SO2CH3    mp 178-8(trans)                           I-37                                                                              1-CH3     H  H  2-CH3-4-SO2CH3                                              I-38                                                                              5,5-(CH3)2                                                                               H  H  2-CH3-4-SO2CH3                                              I-39                                                                              1,5,5-(CH3)3                                                                             H  H  2-CH3-4-SO2CH3                                              I-40                                                                              --(n = 0) CH3                                                                               CH3                                                                               2-CH3-4-SO2CH3                                              I-41                                                                              --        H  H  2-Cl                                                        I-42                                                                              --        H  H  2-Cl-3-CH3-4-Cl                                             I-43                                                                              --        H  H  2-Cl-3-CH3-4-SO2C3H7 (i)                                    I-44                                                                              --        H  H  2-Cl-3-CH3-4-SO2CH3                                         I-45                                                                              --        H  H  2-Cl-3-Cl-4-Cl                                              I-46                                                                              --        H  H  2-Cl-3-Cl-4-SO2C2H5                                         I-47                                                                              --        H  H  2-Cl-3-Cl-4-SO2C3H7 (i)                                     I-48                                                                              --        H  H  2-Cl-3-Cl-4-SO2CH3                                                                               mp 177-180(dec)                           I-49                                                                              5-CH3     H  H  2-Cl-3-Cl-4-SO2CH3                                                                               mp 125-7(trans)                           I-50                                                                              1-CH3     H  H  2-Cl-3-Cl-4-SO2CH3                                                                               powder                                    I-51                                                                              5,5-(CH3)2                                                                               H  H  2-Cl-3-Cl-4-SO2CH3                                          I-52                                                                              1,5,5-(CH3)3                                                                             H  H  2-Cl-3-Cl-4-SO2CH3                                          I-53                                                                              --(n = 0) CH3                                                                               CH3                                                                               2-Cl-3-Cl-4-SO2CH3                                          I-54                                                                              --        H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             mp 157-8                                  I-55                                                                              5-CH3     H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             mp 154-6(trans)                           I-56                                                                              1-CH3     H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             oil                                       I-57                                                                              5,5-(CH3)2                                                                               H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             powder                                    I-58                                                                              1,5,5-(CH3)3                                                                             H  H  2-Cl-3-OCH3-4-SO2CH3                                        I-59                                                                              --(n = 0) CH3                                                                               CH3                                                                               2-Cl-3-OCH3-4-SO2CH3                                        I-60                                                                              --        H  H  2-Cl-3-SO2CH3-4-SO2CH3                                      I-61                                                                              --(n = 0) H  H  2-Cl-4-Cl         mp 97-8                                   I-62                                                                              --        H  H  2-Cl-4-NO2                                                  I-63                                                                              --        H  H  2-Cl-4-OCH3                                                 I-64                                                                              --        H  H  2-Cl-4-SO2C3H7(i)                                           I-65                                                                              --        H  H  2-Cl-4-SO2CH3     mp 146-8                                  I-66                                                                              --        H  H  2-CN                                                        I-67                                                                              --        H  H  2-COOCH3                                                    I-68                                                                              --        H  H  2-COOH                                                      I-69                                                                              --        H  H  2-I                                                         I-70                                                                              --        H  H  2-NO2                                                       I-71                                                                              5-CH3     H  H  2-NO2                                                       I-72                                                                              1-CH3     H  H  2-NO2                                                       I-73                                                                              --(n = 0) H  H  2-NO2-3-CH2OCH3-4-SO2CH3                                    I-74                                                                              --        H  H  2-NO2-3-CH3-4-Cl                                            I-75                                                                              --        H  H  2-NO2-3-CH3-4-SO2CH3                                        I-76                                                                              --        H  H  2-NO2-3-Cl-4-Cl                                             I-77                                                                              --        H  H  2-NO2-3-Cl-4-SCH3                                           I-78                                                                              --        H  H  2-NO2-3-Cl-4-SO2C2H5                                        I-79                                                                              --        H  H  2-NO2-3-Cl-4-SO2CH3                                         I-80                                                                              --        H  H  2-NO2-3-OCH3-4-CH3                                          I-81                                                                              --        H  H  2-NO2-3-OCH3-4-Cl mp 120-1                                  I-82                                                                              --        H  H  2-NO2-3-OCH3-4-OCH3                                         I-83                                                                              --        H  H  2-NO2-3-OCH3-4-SO2CH3                                       I-84                                                                              --        H  H  2-NO2-3-SO2CH3-4-SO2CH3                                     I-85                                                                              --        H  H  2-NO2-4-CF3       powder                                    I-86                                                                              5-CH3     H  H  2-NO2-4-CF3       mp 131-4(trans)                           I-87                                                                              1-CH3     H  H  2-NO2-4-CF3                                                 I-88                                                                              5,5-(CH3)2                                                                               H  H  2-NO2-4-CF3                                                 I-89                                                                              1,5,5-(CH3)3                                                                             H  H  2-NO2-4-CF3                                                 I-90                                                                              --(n = 0) CH3                                                                               CH3                                                                               2-NO2-4-CF3                                                 I-91                                                                              --(n = 0) H  H  2-NO2-4-CH2OCH3                                             I-92                                                                              5-CH3     H  H  2-NO2-4-CH2OCH3                                             I-93                                                                              1-CH3     H  H  2-NO2-4-CH2OCH3                                             I-94                                                                              --(n = 0) H  H  2-NO2-4-CH3       mp 122-4                                  I-95                                                                              5-CH3     H  H  2-NO2-4-CH3                                                 I-96                                                                              1-CH3     H  H  2-NO2-4-CH3                                                 I-97                                                                              --(n = 0) H  H  2-NO2-4-Cl        mp 132-4                                  I-98                                                                              5-CH3     H  H  2-NO2-4-Cl        mp 139-141(trans)                         I-99                                                                              1-CH3     H  H  2-NO2-4-Cl        mp 77-9                                   I-100                                                                             5,5-(CH3)2                                                                               H  H  2-NO2-4-Cl        mp 134-5.5                                I-101                                                                             1,5,5-(CH3)3                                                                             H  H  2-NO2-4-Cl        powder                                    I-102                                                                             --(n = 0) CH3                                                                               CH3                                                                               2-NO2-4-Cl                                                  I-103                                                                             --        H  H  2-NO2-4-CN                                                  I-104                                                                             --        H  H  2-NO2-4-NHCOCH3                                             I-105                                                                             --        H  H  2-NO2-4-NO2                                                 I-106                                                                             --        H  H  2-NO2-4-OC5H11                                              I-107                                                                             --        H  H  2-NO2-4-OCH2OCH3                                            I-108                                                                             --        H  H  2-NO2-4-OCH2OCH3                                            I-109                                                                             --        H  H  2-NO2-4-OCH3      mp 76- 81(dec)                            I-110                                                                             5-CH3     H  H  2-NO2-4-OCH3                                                I-111                                                                             1-CH3     H  H  2-NO2-4-OCH3                                                I-112                                                                             5,5-(CH3)2                                                                               H  H  2-NO2-4-OCH3                                                I-113                                                                             1,5,5-(CH3)3                                                                             H  H  2-NO2-4-OCH3                                                I-114                                                                             --(n = 0) CH3                                                                               CH3                                                                               2-NO2-4-OCH3                                                I-115                                                                             --        H  H  2-NO2-4-ORx                                                 I-116                                                                             --        H  H  2-NO2-4-ORy                                                 I-117                                                                             --        H  H  2-NO2-4-ORz                                                 I-118                                                                             --        H  H  2-NO2-4-SCH(CH3)COOC2H5                                     I-119                                                                             --        H  H  2-NO2-4-SCH2CH2OCH2CH2OCH3                                  I-120                                                                             --        H  H  2-NO2-4-SCH2CH2OCH3                                         I-121                                                                             --(n = 0) H  H  2-NO2-4-SCH2Cl                                              I-122                                                                             --        H  H  2-NO2-4-SCH2CCN                                             I-123                                                                             --        H  H  2-NO2-4-SCH2COCH3                                           I-124                                                                             --        H  H  2-NO2-4-SCH2CCH                                             I-125                                                                             --        H  H  2-NO2-4-SCH2OCH3                                            I-126                                                                             5-CH3     H  H  2-NO2-4-SCH2OCH3  powder(trans)                             I-127                                                                             1-CH3     H  H  2-NO2-4-SCH2OCH3                                            I-128                                                                             5,5-(CH3)2                                                                               H  H  2-NO2-4-SCH2OCH3                                            I-129                                                                             1,5,5-(CH3)3                                                                             H  H  2-NO2-4-SCH2OCH3                                            I-130                                                                             --(n = 0) CH3                                                                               CH3                                                                               2-NO2-4-SCH2OCH3                                            I-131                                                                             --        H  H  2-NO2-4-SCH2Rz                                              I-132                                                                             --        H  H  2-NO2-4-SCH2SCH3                                            I-133                                                                             --        H  H  2-NO2-4-SCH3      mp 98-100                                 I-134                                                                             --        H  H  2-NO2-4-SO2CH(CH3)COOC2H5                                   I-135                                                                             --        H  H  2-NO2-4-SO2CH2Cl                                            I-136                                                                             5-CH3     H  H  2-NO2-4-SO2CH2Cl                                            I-137                                                                             1-CH3     H  H  2-NO2-4-SO2CH2Cl                                            I-138                                                                             5,5-(CH3)2                                                                               H  H  2-NO2-4-SO2CH2Cl                                            I-139                                                                             1,5,5-(CH3)3                                                                             H  H  2-NO2-4-SO2CH2Cl                                            I-140                                                                             --(n = 0) CH3                                                                               CH3                                                                               2-NO2-4-SO2CH2Cl                                            I-141                                                                             --        H  H  2-NO2-4-SO2CH2COOCH3                                        I-142                                                                             --        H  H  2-NO2-4-SO2CH2OCH3                                          I-143                                                                             --        H  H  2-NO2-4-SO2CH3    mp 161-2                                  I-144                                                                             5-CH3     H  H  2-NO2-4-SO2CH3    mp 164-5(dec)(trans)                      I-145                                                                             1-CH3     H  H  2-NO2-4-SO2CH3    powder                                    I-146                                                                             5,5-(CH3)2                                                                               H  H  2-NO2-4-SO2CH3    mp 159-161                                I-147                                                                             1,5,5-(CH3)3                                                                             H  H  2-NO2-4-SO2CH3                                              I-148                                                                             --(n = 0) CH3                                                                               CH3                                                                               2-NO2-4-SO2CH3                                              I-149                                                                             --        H  H  2-NO2-4-SO2CH3-5-Cl                                         I-150                                                                             --        H  H  2-NO2-4-SO2CHCl2                                            I-151                                                                             --(n = 0) H  H  2-NO2-4-SPh                                                 I-152                                                                             --        H  H  2-NO2-4-SRz                                                 I-153                                                                             --        H  H  2-NO2-5-CH3                                                 I-154                                                                             --        H  H  2-OCH3                                                      I-155                                                                             --        H  H  2-OCH3-3-OCH3-4-OCH3                                        I-156                                                                             --        H  H  2-Ph                                                        I-157                                                                             --        H  H  2-SCF3                                                      I-158                                                                             --        H  H  2-SCH3                                                      I-159                                                                             --        H  H  2-SO2CF3                                                    I-160                                                                             --        H  H  2-SO2CCH3                                                   I-161                                                                             --        H  H  2-SO2CCH3-4-NO2                                             I-162                                                                             --        H  H  2-SOCF3                                                     I-163                                                                             5-CH3     H  H  2-Cl-4-Cl         mp 86.5-9.5(trans)                        I-164                                                                             1-CH3     H  H  2-Cl-4-Cl         mp 92-4                                   I-165                                                                             6-CH3     H  H  2-NO2-4-Cl        nD 25.5 1.6050                            I-166                                                                             --(n = 0) CH3                                                                               H  2-NO2-4-Cl        mp 107-9                                  I-167                                                                             --        H  H  2-CH3-4-CH3       mp 83-6                                   I-168                                                                             5-CH3     H  H  2-Cl-3-OCH3-4-SO2C2H5                                                                            mp 120-2(trans)                           I-169                                                                             5,6-(CH3)2                                                                               H  H  2-NO2-4-Cl        powder                                    I-170                                                                             5-CH3     H  H  2-Cl-3-CH3-4-SO2CH3                                                                              mp 157-9(trans)                           I-171                                                                             5-CH3-5-COOC2H5                                                                          H  H  2-NO2             mp 133.5-4.5(trans)                       I-172                                                                             5-CH3     H  H  2-Cl-4-SO2CH3     mp 129-14 131(trans)                      I-173                                                                             5-CH3     H  H  2-Cl-4-SO2CH3-5-Cl                                                                               mp 141-4(trans)                           I-174                                                                             5,6-(CH3)2                                                                               H  H  2-NO2-4-SO2CH3    powder                                    I-175                                                                             6-CH3     H  H  2-NO2-4-SO2CH3    oil                                       I-176                                                                             5,6-(CH3)2                                                                               H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             powder                                    I-177                                                                             5-CH3     H  H  2-CH3-3-Br-4-SO2CH3                                                                              mp 183-5(trans)                           I-178                                                                             1-CH3     H  H  2-CH3-3-Br-4-SO2CH3                                                                              powder                                    I-179                                                                             5-CH3     H  H  2-Cl-3-CH2OCH3-4-SO2CH3                                                                          powder (trans)                            I-180                                                                             1-CH3     H  H  2-Cl-3-CH2OCH3-4-SO2CH3                                                                          powder                                    I-181                                                                             1,5-(CH3)2                                                                               H  H  2-NO2-4-Cl        mp 122-3                                  I-182                                                                             5-CH3     H  H  2-Cl-4-SO2CH3-5-OCH3                                                                             powder(trans)                             I-183                                                                             5-CH3     H  H  2-Cl-3-OCH2CHCH2-4-SO2CH3                                                                        powder(trans)                             I-184                                                                             5-CH3     H  H  2-Cl-3-CO2CH3-4-SO2CH3                                      I-185                                                                             5-CH3     H  H  2-Cl--4-CF3       nD 25.5 1.5369(trans)                     I-186                                                                             5-CH3     H  H  2-Cl-3-OCH2(Br)CCH2-4-SO2CH3                                                                     powder(trans)                             I-187                                                                             5-CH3     H  H  2-Cl-3-OCH2CCH-4-SO2CH3                                                                          mp 184-7(trans)                           I-188                                                                             5-CH3     H  H  2-Cl-3-OCH2Cl-4-SO2CH3                                                                           mp 103-5(trans)                           I-189                                                                             5-CH3-5-CO2C2H5                                                                          H  H  2-CH3-3-CH3-4-SO2CH3                                                                             oil(trans)                                I-190                                                                             5-CH3     H  H  2-Cl-3-OC2H5-4-SO2CH3                                                                            powder(trans)                             I-191                                                                             5-CH(CH3)2                                                                               H  H  2-NO2-4-Cl        mp 161-2(trans)                           I-192                                                                             5-CH3     H  H  2-CH3-3-CH3-4-SO2CH3                                                                             mp 164-7(cis)                             I-193                                                                             5-CH3     H  H  2-Cl-4-OCF3       nD 25.5 1.5248(trans)                     I-194                                                                             5-CH3     H  H  2-CH(CH3)2040Cl   nD 25.0 1.5710(trans)                     I-195                                                                             5-CH3     H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             mp 132-5(cis)                             I-196                                                                             5-CH3     H  H  2-CH2OCH3-4-SO2CH3                                                                               nD 24.5 1.5662(trans)                     I-197                                                                             5-C2H5    H  H  2-NO2-4-Cl        mp 109-111(trans)                         I-198                                                                             5-CH(CH3)2                                                                               H  H  2-NO2-4-SO2CH3    mp 88-90(trans)                           I-199                                                                             5-CH3-5-CO2C2H5                                                                          H  H  2-NO2-4-SO2CH3                                              I-200                                                                             5-CH3     H  H  2-Cl-3-CH3-4-SO2CH3                                                                              powder(cis)                               I-201                                                                             5-CH3     H  H  2-NO2-4-SO2CF2H   mp 176-8(dec)(trans)                      I-202                                                                             5-CH3-5-CO2C2H5                                                                          H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             nD 24.5 1.5649(trans)                     I-203                                                                             5-OCH3    H  H  2-NO2-4-SO2CH3    powder(trans)                             I-204                                                                             5-CH3     H  H  2-Cl-4-SO2CH3     powder(cis)                               I-205                                                                             5-CH3     H  H  2-CH3-3-Cl-4-SO2CH3                                                                              mp 165-7(trans)                           I-206                                                                             5-CH3     H  H  2-NO2-4-COCH3     mp 146-8(trans)                           I-207                                                                             5-CH3     H  H  2-Cl-4-OCHF2      nD 24 1.5592(trans)                       I-208                                                                             5-CH3     H  H  2-CH3-3-Br-4-SO2CH3                                                                              mp 172-4(cis)                             I-209                                                                             5-CH3     H  H  2-Cl-3-Cl-4-SO2CH3                                                                               powder(cis)                               I-210                                                                             5,5-(CH3)2-6-CH3                                                                         H  H  2-NO2-4-SO2CH3    mp 175-7                                  I-211                                                                             1-CH3     H  H  2-NO2-3-OCH3-4-Cl powder                                    I-212                                                                             5-CH3     H  H  2-NO2-3-OCH3-4-Cl powder(trans)                             I-213                                                                             1-SCH3    H  H  2-NO2-4-Cl        mp 168-170                                I-214                                                                             5-CH3     H  H  2-CL-3-Cl-4-SO2CH3                                                                               Na salt 180(dec)(trans)                   I-215                                                                             5-CH3     H  H  2-Cl-4-OCF2CHF2   nD 25.5 1.5276(trans)                     I-216                                                                             5-CH3     H  H  2-NO2-4-CHF2      mp 163-5(trans)                           I-217                                                                             5-CH3     H  H  2-NO2-4-SO2CH3    powder(cis)                               I-218                                                                             5-CH3     H  H  2-CH3-3-NO2-4-SO2CH3                                                                             mp 197-9(trans)                           I-219                                                                             5-CH3-5-SO2CH3                                                                           H  H  2-NO2-4-Cl        mp 184-6                                  I-220                                                                             5-CH3-5-SCH3                                                                             H  H  2-NO2-4-Cl        mp 144-5                                  I-221                                                                             5-CH3     H  H  2-NO2-4-CF3       mp 90-2(cis)                              I-222                                                                             5-CH3     H  H  2-NO2--3-CH3-4-SO2CH3                                                                            mp 139-141(trans)                         I-223                                                                             5-CH3-5-CO2C2H5                                                                          H  H  2-NO2-4-CF3       oil                                       I-224                                                                             5-CH3     H  H  2-NO2-4-Cl        mp 104-8(cis)                             I-225                                                                             5-CH3     H  H  2-OCH3-3-OCH3-4-OCH3                                                                             powder(trans)                             I-226                                                                             5-CH3     H  H  2-Cl-3-Cl-4-Cl    mp 111-2(trans)                           I-227                                                                             5-CH3     H  H  2-Cl-3-Cl-4-OCH3  mp 113-4(trans)                           I-228                                                                             5-Br      H  H  2-NO2-4-Cl        mp 158-160(trans)                         I-229                                                                             5-CH2CH2OCH3                                                                             H  H  2-NO2-4-Cl        nD 23 1.5850(trans)                       I-230                                                                             5-SCH2CH3 H  H  2-NO2-4-Cl        mp 119-120(trans)                         I-231                                                                             5-CH3     H  H  2-NO2-4-SO2N(CH3)2                                                                               mp 142-5(dec)(trans)                      I-232                                                                             5-CH3     H  H  2-CH3-3-CH3-4-SO2CH3                                                                             H2NCH3 salt mp 139-140(dec)(trans)        I-233                                                                             5-CH3     H  H  2-CH3-3-CH3-4-SO2CH3                                                                             Na salt mp 168(dec)(trans)                I-234                                                                             5-CH3     H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             Na salt mp 158(dec)(cis)                  I-235                                                                             5-CH3     H  H  2-CH3-3-CH3-4-Cl  mp 117-8(trans)                           I-236                                                                             5-CH3     H  H  2-NO2-4-NO2       mp 151-2(trans)                           I-237                                                                             5-CH3     H  H  2-NO2-4-SCH3      mp 129-132(trans)                         I-238                                                                             1-CH3     H  H  2-NO2-4-SHC3      mp 70-4                                   I-239                                                                             5,5-(Br)2 H  H  2-CH3-3-CH3-4-SO2CH3                                                                             mp 129-131                                I-240                                                                             5-SCH2CH3 H  H  2-CH3-3-CH3-4-SO2CH3                                                                             mp 140-2(trans)                           I-241                                                                             5-CH2CH2OCH3                                                                             H  H  2-NO2-4-SO2CH3    powder(trans)                             I-242                                                                             5-CH3     H  H  2-NO2-4-ORx       powder(trans)                             I-243                                                                             5-CH3     H  H  2-CH3-3-Cl-4-OCH3 mp 115-7(trans)                           I-244                                                                             5-CH3     H  H  2-OCH3-4-SO2CH3   powder(trans)                             I-245                                                                             5-CH3     H  H  2-CF3-4-SO2CH3    powder(trans)                             I-246                                                                             5-CH3     H  H  2-NO2-4-SCH2SCH3  powder(trans)                             I-247                                                                             5-CH3     H  H  2-NO2-4-SO2CH2OCH3                                                                               mp 147-150(trans)                         I-248                                                                             5-SO2CH2CH3                                                                              H  H  2-NO2-4-Cl        mp 163-5(trans)                           I-249                                                                             5-CH3     H  H  2-CF3-4-Cl        powder(trans)                             I-250                                                                             1-CH3     H  H  2-CF3-4-Cl        powder                                    I-251                                                                             1-CH2CH2OCH3                                                                             H  H  2-NO2-4-Cl        nD 23 1.5842                              I-252                                                                             1-CH3     H  H  2-NO2-4-NO2       powder                                    I-253                                                                             1-CH3     H  H  2-NO2-4-Orx       powder                                    I-254                                                                             1-CH3     H  H  2-CF3-4-SO2CH3    powder                                    I-255                                                                             1-CH3     H  H  2-NO2-4-SCH2OCH3  powder                                    I-256                                                                             5-CH3     H  H  2-Cl-3-Cl-4-OCH2OCH3                                                                             powder(trans)                             I-257                                                                             --(N = 0) H  H  2-NO2-4-SCH2OCH3  powder                                    I-258                                                                             5-CH3     H  H  2-OC2H5-3-Cl-4-SO2CH3                                                                            mp 152-6(cis)                             I-259                                                                             --(N = 0) H  H  2-NO2-4-NHCOCH3   powder                                    I-260                                                                             --        H  H  2-NO2-4-SCH2CHCH2 oil                                       I-261                                                                             5-CH3     H  H  2-F-3-F-4-F-5-F   mp 172-4(trans)                           I-262                                                                             5-CH3     H  H  2-CH3-3-CH3-4-SO2CH3                                                                             Na salt mp 230(dec)(cis)                  I-263                                                                             5-CH3     H  H  2-Cl-3-CH3-4-SO2CH3                                                                              Na salt mp 180-2(dec)(cis)                I-264                                                                             5-CH3     H  H  2-CH3-3-Br-4-SO2CH3                                                                              Na salt mp 223(dec)(cis)                  I-265                                                                             5-CH3     H  H  2-Cl-3-Cl-4-OCH2SCH3                                                                             powder(trans)                             I-266                                                                             5-CH3     H  H  2-Cl-3-Cl-4-OCH2Ph                                                                               mp 148-9(trans)                           I-267                                                                             5-CH3     H  H  2-Cl-3-Cl-4-OH    mp 169-171(dec)(trans)                    I-268                                                                             5-CH3     H  H  2-CH3-3-CH3-4-SO2CH3                                                                             K salt mp 198-200(dec)(trans)             I-269                                                                             5-CH3     H  H  2-CH3-3-CH3-4-SO2CH3                                                                             Li salt mp > 260(trans)                   I-270                                                                             5-CH3     H  H  2-CH3-3-CH3-4-SO2CH3                                                                             1/2 Ca salt mp > 260(trans)               I-271                                                                             5-CH3     H  H  2-CH3-3-CH3-4-SO2CH3                                                                             1/2 Cu salt mp > 260(trans)               I-272                                                                             5-CH3     H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             K salt mp 188-190(dec)(cis)               I-273                                                                             5-CH3     H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             Li salt mp 178-180(dec)(cis)              I-274                                                                             5-CH3     H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             1/2 Ca salt mp > 225(dec)(cis)            I-275                                                                             5-CH3     H  H  2-Cl-3-OCH3-4-SO2CH3                                                                             1/2 Cu salt mp 210-212(cis)               __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________     Structural                                                                      ##STR9##                                                                      No. (R2)n R3 R4 Hetero ring                                                                           Xm         Physical Properties                          __________________________________________________________________________     II-1                                                                               5-CH3 H  H  2-pyridine                                                                            5-CF3                                                   II-2                                                                               5-CH3 H  H  2-pyridine                                                                            5-CH2OCH3                                               II-3                                                                               5-CH3 H  H  2-pyridine                                                                            5-CH2SCH3                                               II-4                                                                               5-CH3 H  H  2-pyridine                                                                            5-SCH3                                                  II-5                                                                               5-CH3 H  H  2-pyridine                                                                            5-SOCH3                                                 II-6                                                                               5-CH3 H  H  2-pyridine                                                                            5-SO2CH3                                                II-7                                                                               5-CH3 H  H  2-pyridine                                                                            5-SC2H5                                                 II-8                                                                               5-CH3 H  H  2-pyridine                                                                            5-SOC2H5                                                II-9                                                                               5-CH3 H  H  2-pyridine                                                                            5-SO2C2H5                                               II-10                                                                              5-CH3 H  H  2-pyridine                                                                            5-CH3                                                   II-11                                                                              5-CH3 H  H  2-pyridine                                                                            5-NO2                                                   II-12                                                                              5-CH3 H  H  2-pyridine                                                                            5-CN                                                    II-13                                                                              6-CH3 H  H  2-pyridine                                                                            5-CF3                                                   II-14                                                                              6-CH3 H  H  2-pyridine                                                                            5-CH2OCH3                                               II-15                                                                              6-CH3 H  H  2-pyridine                                                                            5-CH2SCH3                                               II-16                                                                              6-CH3 H  H  2-pyridine                                                                            5-SCH3                                                  II-17                                                                              6-CH3 H  H  2-pyridine                                                                            5-SOCH3                                                 II-18                                                                              6-CH3 H  H  2-pyridine                                                                            5-SO2CH3                                                II-19                                                                              6-CH3 H  H  2-pyridine                                                                            5-SC2H5                                                 II-20                                                                              6-CH3 H  H  2-pyridine                                                                            5-SOC2H5                                                II-21                                                                              6-CH3 H  H  2-pyridine                                                                            5-SO2C2H5                                               II-22                                                                              6-CH3 H  H  2-pyridine                                                                            5-CH3                                                   II-23                                                                              6-CH3 H  H  2-pyridine                                                                            5-NO2                                                   II-24                                                                              6-CH3 H  H  2-pyridine                                                                            5-CN                                                    II-25                                                                              --(n = 0)                                                                            H  H  2-pyridine                                                                            5-CF3                                                   II-26                                                                              --    H  H  2-pyridine                                                                            5-CH2OCH3                                               II-27                                                                              --    H  H  2-pyridine                                                                            5-CH2SCH3                                               II-28                                                                              --    H  H  2-pyridine                                                                            5-SCH3                                                  II-29                                                                              --    H  H  2-pyridine                                                                            5-SOCH3                                                 II-30                                                                              --    H  H  2-pyridine                                                                            5-SO2CH3                                                II-31                                                                              --(n = 0)                                                                            H  H  2-pyridine                                                                            5-SC2H5                                                 II-32                                                                              --    H  H  2-pyridine                                                                            5-SOC2H5                                                II-33                                                                              --    H  H  2-pyridine                                                                            5-SO2C2H5                                               II-34                                                                              --    H  H  2-pyridine                                                                            5-CH3                                                   II-35                                                                              --    H  H  2-pyridine                                                                            5-NO2                                                   II-36                                                                              --    H  H  2-pyridine                                                                            5-CN                                                    II-37                                                                              1-CH3 H  H  2-pyridine                                                                            5-CF3                                                   II-38                                                                              1-CH3 H  H  2-pyridine                                                                            5-CH2OCH3                                               II-39                                                                              1-CH3 H  H  2-pyridine                                                                            5-CH2SCH3                                               II-40                                                                              1-CH3 H  H  2-pyridine                                                                            5-SCH3                                                  II-41                                                                              1-CH3 H  H  2-pyridine                                                                            5-SOCH3                                                 II-42                                                                              1-CH3 H  H  2-pyridine                                                                            5-SO2CH3                                                II-43                                                                              1-CH3 H  H  2-pyridine                                                                            5-SC2H5                                                 II-44                                                                              1-CH3 H  H  2-pyridine                                                                            5-SOC2H5                                                II-45                                                                              1-CH3 H  H  2-pyridine                                                                            5-SO2C2H5                                               II-46                                                                              1-CH3 H  H  2-pyridine                                                                            5-CH3                                                   II-47                                                                              1-CH3 H  H  2-pyridine                                                                            5-NO2                                                   II-48                                                                              1-CH3 H  H  2-pyridine                                                                            5-CN                                                    II-49                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CF3                                                   II-50                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CH2OCH3                                               II-51                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CH2SCH3                                               II-52                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SCH3                                                  II-53                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SOCH3                                                 II-54                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SO2CH3                                                II-55                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SC2H5                                                 II-56                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SOC2H5                                                II-57                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SO2C2H5                                               II-58                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CH3                                                   II-59                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-NO2                                                   II-60                                                                              5-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CN                                                    II-61                                                                              --(n = 0)                                                                            CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CF3                                                   II-62                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CH2OCH3                                               II-63                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CH2SCH3                                               II-64                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SCH3                                                  II-65                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SOCH3                                                 II-66                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SO2CH3                                                II-67                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SC2H5                                                 II-68                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SOC2H5                                                II-69                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SO2C2H5                                               II-70                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CH3                                                   II-71                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-NO2                                                   II-72                                                                              --    CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CN                                                    II-73                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CF3                                                   II-74                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CH2OCH3                                               II-75                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CH2SCH3                                               II-76                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SCH3                                                  II-77                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SOCH3                                                 II-78                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SO2CH3                                                II-79                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SC2H5                                                 II-80                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SOC2H5                                                II-81                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-SO2C2H5                                               II-82                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CH3                                                   II-83                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-NO2                                                   II-84                                                                              1-CH3 CH3                                                                               CH3                                                                               2-pyridine                                                                            5-CN                                                    II-85                                                                              5-CH3 H  H  3-pyridine                                                                            2-CF3                                                   II-86                                                                              5-CH3 H  H  3-pyridine                                                                            2-CF3-6-Cl                                              II-87                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2OCH3                                               II-88                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2OCH3-6-CH3                                         II-89                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2OCH3-6-Cl                                          II-90                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2OCH3-6-SCH3                                        II-91                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2SCH3                                               II-92                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2SCH3-6-CH3                                         II-93                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2SCH3-6-Cl                                          II-94                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2SO2CH3                                             II-95                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2SO2CH3-6-CH3                                       II-96                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-97                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-98                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH3                                                   II-99                                                                              5-CH3 H  H  3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-100                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-101                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-CH3                                             II-102                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-Cl mp 140-1(trans)                              II-103                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-CN                                              II-104                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-OCH3                                            II-105                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-SCH2Cl                                          II-106                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-SCH2OCH3                                        II-107                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-SCH3                                            II-108                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-SO2CH2Cl                                        II-109                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-SO2CH3                                                                            mp 162-4(trans)                              II-110                                                                             5-CH3 H  H  3-pyridine                                                                            2-CN                                                    II-111                                                                             5-CH3 H  H  3-pyridine                                                                            2-CN-6-CH3                                              II-112                                                                             5-CH3 H  H  3-pyridine                                                                            2-CN-6-Cl                                               II-113                                                                             --(n =  0)                                                                           H  H  3-pyridine                                                                            2-CF3                                                   II-114                                                                             --    H  H  3-pyridine                                                                            2-CF3-6-Cl                                              II-115                                                                             --    H  H  3-pyridine                                                                            2-CH2OCH3                                               II-116                                                                             --    H  H  3-pyridine                                                                            2-CH2OCH3-6-CH3                                         II-117                                                                             --    H  H  3-pyridine                                                                            2-CH2OCH3-6-Cl                                          II-118                                                                             --    H  H  3-pyridine                                                                            2-CH2OCH3-6-SCH3                                        II-119                                                                             --    H  H  3-pyridine                                                                            2-CH2SCH3                                               II-120                                                                             --    H  H  3-pyridine                                                                            2-CH2SCH3-6-CH3                                         II-121                                                                             --(n = 0)                                                                            H  H  3-pyridine                                                                            2-CH2SCH3-6-Cl                                          II-122                                                                             --    H  H  3-pyridine                                                                            2-CH2SO2CH3                                             II-123                                                                             --    H  H  3-pyridine                                                                            2-CH2SO2CH3-6-CH3                                       II-124                                                                             --    H  H  3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-125                                                                             --    H  H  3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-126                                                                             --    H  H  3-pyridine                                                                            2-CH3                                                   II-127                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-128                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-129                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-CH3                                             II-130                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-Cl mp 109-111                                   II-131                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-CN                                              II-132                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-OCH3                                            II-133                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-SCH2Cl                                          II-134                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-SCH2OCH3                                        II-135                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-SCH3                                            II-136                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-SO2CH2Cl                                        II-137                                                                             --    H  H  3-pyridine                                                                            2-CH3-6-SO2CH3                                                                            mp 163-5                                     II-138                                                                             --    H  H  3-pyridine                                                                            2-CN                                                    II-139                                                                             --    H  H  3-pyridine                                                                            2-CN-6-CH3                                              II-140                                                                             --    H  H  3-pyridine                                                                            2-CN-6-Cl                                               II-141                                                                             1-CH3 H  H  3-pyridine                                                                            2-CF3                                                   II-142                                                                             1-CH3 H  H  3-pyridine                                                                            2-CF3-6-Cl                                              II-143                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2OCH3                                               II-144                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2OCH3-6-CH3                                         II-145                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2OCH3-6-Cl                                          II-146                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2OCH3-6-SCH3                                        II-147                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2SCH3                                               II-148                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2SCH3-6-CH3                                         II-149                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2SCH3-6-Cl                                          II-150                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2SO2CH3                                             II-151                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2SO2CH3-6-CH3                                       II-152                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-153                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-154                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3                                                   II-155                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-156                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-157                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-CH3                                             II-158                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-Cl                                              II-159                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-CN                                              II-160                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-OCH3                                            II-161                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-SCH2Cl                                          II-162                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-SCH2OCH3                                        II-163                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-SCH3                                            II-164                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-SO2CH2Cl                                        II-165                                                                             1-CH3 H  H  3-pyridine                                                                            2-CH3-6-SO2CH3                                                                            oil                                          II-166                                                                             1-CH3 H  H  3-pyridine                                                                            2-CN                                                    II-167                                                                             1-CH3 H  H  3-pyridine                                                                            2-CN-6-CH3                                              II-168                                                                             1-CH3 H  H  3-pyridine                                                                            2-CN-6-Cl                                               II-169                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CF3                                                   II-170                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CF3-6-Cl                                              II-171                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3                                               II-172                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3-6-CH3                                         II-173                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3-6-Cl                                          II-174                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3-6-SCH3                                        II-175                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SCH3                                               II-176                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SCH3-6-CH3                                         II-177                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SCH3-6-Cl                                          II-178                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3                                             II-179                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3-6-CH3                                       II-180                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-181                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-182                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3                                                   II-183                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-184                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-185                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CH3                                             II-186                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-Cl                                              II-187                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CN                                              II-188                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-OCH3                                            II-189                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SCH2Cl                                          II-190                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SCH2OCH3                                        II-191                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SCH3                                            II-192                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SO2CH2Cl                                        II-193                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SO2CH3                                          II-194                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CN                                                    II-195                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CN-6-CH3                                              II-196                                                                             5-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CN-6-Cl                                               II-197                                                                             --(n = 0)                                                                            CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CF3                                                   II-198                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CF3-6-Cl                                              II-199                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3                                               II-200                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3-6-CH3                                         II-201                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3-6-Cl                                          II-202                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3-6-SCH3                                        II-203                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SCH3                                               II-204                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SCH3-6-CH3                                         II-205                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SCH3-6-Cl                                          II-206                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3                                             II-207                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3-6-CH3                                       II-208                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-209                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-210                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3                                                   II-211                                                                             --(n = 0)                                                                            CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-212                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-213                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CH3                                             II-214                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-Cl                                              II-215                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CN                                              II-216                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-OCH3                                            II-217                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SCH2Cl                                          II-218                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SCH2OCH3                                        II-219                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SCH3                                            II-220                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SO2CH2Cl                                        II-221                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SO2CH3                                          II-222                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CN                                                    II-223                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CN-6-CH3                                              II-224                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CN-6-Cl                                               II-225                                                                             --    CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CF3                                                   II-226                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CF3-6-Cl                                              II-227                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3                                               II-228                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3-6-CH3                                         II-229                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3-6-Cl                                          II-230                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2OCH3-6-SCH3                                        II-231                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SCH3                                               II-232                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SCH3-6-CH3                                         II-233                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SCH3-6-Cl                                          II-234                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3                                             II-235                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3-6-CH3                                       II-236                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-237                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH2SO2CH3-6-Cl                                        II-238                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3                                                   II-239                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-240                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CH2SCH3                                         II-241                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CH3                                             II-242                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-Cl                                              II-243                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-CN                                              II-244                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-OCH3                                            II-245                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SCH2Cl                                          II-246                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SCH2OCH3                                        II-247                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SCH3                                            II-248                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SO2CH2Cl                                        II-249                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CH3-6-SO2CH3                                          II-250                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CN                                                    II-251                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CN-6-CH3                                              II-252                                                                             1-CH3 CH3                                                                               CH3                                                                               3-pyridine                                                                            2-CN-6-Cl                                               II-253                                                                             --(n = 0)                                                                            H  H  2-pyrimidine                                                                          5-CF3                                                   II-254                                                                             --    H  H  2-pyrimidine                                                                          5-SCH3                                                  II-255                                                                             --    H  H  2-pyrimidine                                                                          5-SOCH3                                                 II-256                                                                             --    H  H  2-pyrimidine                                                                          5-SO2CH3                                                II-257                                                                             --    H  H  5-pyrimidine                                                                          4-CH3-2-SCH3                                            II-258                                                                             --    H  H  5-pyrimidine                                                                          4-CH3-2-OCH3                                            II-259                                                                             --    H  H  5-pyrimidine                                                                          4-CH3-2-CH3                                             II-260                                                                             --    H  H  5-pyrimidine                                                                          4-CH3-2-CF3                                             II-261                                                                             --    H  H  5-pyrimidine                                                                          4-CH3-2-C2H5                                            II-262                                                                             --    H  H  5-pyrimidine                                                                          4-OCH3-2-SCH3                                           II-263                                                                             --    H  H  5-pyrimidine                                                                          4-OCH3-2-OCH3                                           II-264                                                                             --    H  H  5-pyrimidine                                                                          4-OCH3-2-CH3                                            II-265                                                                             --    H  H  5-pyrimidine                                                                          4-OCH3-2-CF3                                            II-266                                                                             --    H  H  5-pyrimidine                                                                          4-OCH3-2-C2H5                                           II-267                                                                             --    H  H  5-pyrimidine                                                                          4-SCH3-2-SCH3                                           II-268                                                                             --    H  H  5-pyrimidine                                                                          4-SCH3-2-OCH3                                           II-269                                                                             --    H  H  5-pyrimidine                                                                          4-SCH3-2-CH3                                            II-270                                                                             --    H  H  5-pyrimidine                                                                          4-SCH3-2-CF3                                            II-271                                                                             --(n = 0)                                                                            H  H  5-pyrimidine                                                                          4-SCH3-2-C2H5                                           II-272                                                                             --    H  H  5-pyrimidine                                                                          4-CF3-2-SCH3                                            II-273                                                                             --    H  H  5-pyrimidine                                                                          4-CF3-2-OCH3                                            II-274                                                                             --    H  H  5-pyrimidine                                                                          4-CF3-2-CH3                                             II-275                                                                             --    H  H  5-pyrimidine                                                                          4-CF3-2-CF3                                             II-276                                                                             --    H  H  5-pyrimidine                                                                          4-CF3-2-C2H5                                            II-277                                                                             5-CH3 H  H  3-pyridine                                                                            2-CH3-6-Cl mp 93-6(cis)                                 II-278                                                                             5-CH3 H  H  5-thiazole                                                                            2-OCH3-4-CH3                                                                              powder(trans)                                II-279                                                                             1-CH3 H  H  3-pyrazole                                                                            1(N)-CH3-4-NO2                                                                            mp 158-160                                   __________________________________________________________________________

                  TABLE 3                                                          ______________________________________                                         Structural Formula                                                              ##STR10##                                                                     No.   R1      (R2)n      R3   R4   Physical Properties                         ______________________________________                                         III-1 CH3     1,5,5-(CH3)3                                                                              H    H                                                III-2 C2H5    1,5,5-(CH3)3                                                                              H    H                                                III-3 C3H7    1,5,5-(CH3)3                                                                              H    H                                                III-4 CH3     5,5-(CH3)2 H    H                                                III-5 C2H5    5,5-(CH3)2 H    H                                                III-6 C3H7    5,5-(CH3)2 H    H                                                III-7 CH3     5-CH3      H    H                                                III-8 C2H5    5-CH3      H    H                                                III-9 C3H7    5-CH3      H    H                                                III-10                                                                               CH3     1-CH3      H    H                                                III-11                                                                               C2H5    1-CH3      H    H                                                III-12                                                                               C3H7    1-CH3      H    H                                                III-13                                                                               CH3     --(n = 0)  H    H    nD 25.0 1.5489                              III-14                                                                               C2H5    --         H    H                                                III-15                                                                               C3H7    --         H    H    nD 25.0 1.5260                              III-16                                                                               CH3     --         CH3  CH3                                              III-17                                                                               C2H5    --         CH3  CH3                                              III-18                                                                               C3H7    --         CH3  CH3                                              III-19                                                                               CH2Rx   --         H    H    nD 25.0 1.5810                              ______________________________________                                    

As mentioned previously, the compounds possess superior herbicidal activity. The compounds may be applied directly to the soil as pre-emergence treatment or to plant foliage as post-emergence treatment, or they can be mixed intimately with soil. The compounds may be applied to soil or to plant foliage in amount of 1 g or more per 10 are.

A herbicidal composition having a compound of this invention as its active ingreadient may be formulated by mixing suitable carriers in a form generally used in agricultural chemicals such as wettable powder, water soluble powder, granule, emulsifiable concentrate and flowable. As solid carriers, talc, white carbon (silica), bentonite, clay, diatomaceous earth or the like may be used. As liquid carriers, water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, cyclohexanone, dimethylformamide or the like may be used. A surface active agent may, if necessary, be added in order to give a homogeneous and stable formulation.

Compounds can also be applied admixed with other chemicals, which are used in agronomic and horticultural management and which are compatible with such compounds. Such chemicals can be, but are not restricted to, the classes of chemical commonly known as fungicides, insecticides, acaricides, herbicides and plant growth regulators. In particular, by mixing it with the other herbicides, its applied dosage and manpower can be decreased and furthermore, the higher effect by synergetic function of both chemicals can be expected. For admixture of the compound with known herbicides, the use is recomended of benthiocarb, molinate, MY-93(S-(2,2-dimethylbenyil) 1-piperidinecarbothioate) or other carbamate-type herbicides; thiocarbamate-type herbicides; butachlor, pretilachlor, mefenacet or other acid amide-type herbicides; chlormethoxynil, bifenox or other diphenylether-type herbicides; atrazine, cyanazine or other triazine-type herbicides; chlorsulfurnon, sulfometuron-methyl or other sulfonylurea-type herbicides; MCP, MCPB or other phenoxy alkane carboxylic acid-type herbicides; diclofop-methyl or other phenoxy propionic acid-type herbicides; benzoylprop-ethyl, flamprop-ethyl or other benzoylaminopropionic acid-type herbicides; and, as others, piperophos, dymron, bentazon, difenzoquart, naproanilid, HW-52 (4-ethoxy methoxy benzo-2', 3'-dichloroanilide), KNW-242 (1-(3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide), quinclorac (3,7-dichloro-8-quinoline carboxylic acid), and further, sethoxydim, alloxydim-sodium and other cyclohexanedione-type herbicides. These herbicides in various combinations may also be mixed with a vegetable oil or an oil concentrate.

The concentration of the active ingredient in a herbicidal composition may vary according to type of formulation, and the concentration is, for example, in the range of 5-70 weight percent, preferably 10-30 weight percent, in wettable powder; 3-70 weight percent, preferably 5-20 weight percent, in emulsifiable concentrate; 0.01-30 weight percent, preferably 0.05-10 weight percent, in granule.

A wettable powder, or an emulsifiable concentrate thus produced may be diluted with water to a specified concentration and used as a liquid suspension or a liquid emulsion for treating soils or plant foliage. Further, a granule may be directly applied for soil or mixed with soil.

Non-limiting examples of herbicidal composition are illustrated by the following Examples:

EXAMPLE 3: Wettable powder

    ______________________________________                                                          parts by weight                                               ______________________________________                                         Compound of this invention                                                                        20                                                          White carbon       20                                                          Diatomaceous earth 52                                                          Sodium alkylsulfate                                                                                8                                                          ______________________________________                                    

These are mixed homogeneously and reduced to fine particles to provide a wettable powder containing 20% of active ingredient. In use, it is diluted to a desired concentration with water, and is sprayed as suspension.

EXAMPLE 4: Emulsifiable concentrate

    ______________________________________                                                           parts by weight                                              ______________________________________                                         Compound of this invention                                                                         20                                                         Xylene              55                                                         dimethylformamide   15                                                         Polyoxyethylene phenyl ether                                                                       10                                                         ______________________________________                                    

These are mixed and dissolved to provide an emulsifiable concentrate containing 20% of active ingredient. In use, it is diluted to a desired concentration with water, and sprayed as an emulsion.

EXAMPLE 5: Granule

    ______________________________________                                                          parts by weight                                               ______________________________________                                         Compound of this invention                                                                         5                                                          Talc               40                                                          Clay               38                                                          Bentonite          10                                                          sodium alkyl sulfate                                                                               7                                                          ______________________________________                                    

These are mixed homogeneously to provide a granule containing 5% of active ingredient.

Industrial Applicability:

The herbicidal effects of compounds are illustrated by the following test:

Test 1: Postemergence treatment test

Seeds of Henry crabgrass, giant foxtail, rice flatsedge, velvetleaf, redroot pigweed and corn were planted in clay pots (200 cm²) containing clay loam soil and were allowed to grow in greenhouse. When the plants were grown to a 5-10 cm height, aqueous suspensions, prepared by diluting an emulsifiable concentrate with water to specified concentration (250 ppm), were sprayed on the foliage of the plants at a rate of 100 1/10a by using a micro-sprayer.

Three weeds after treatment, the degree of damage of the each plants was observed and evaluated on the scale of value of 0-10, which has the following meanings.

    ______________________________________                                         Index       Degree of damage                                                   ______________________________________                                         0             0%                                                               2           20-29%                                                             4           40-40%                                                             6           60-69%                                                             8           80-89%                                                             10           100%                                                              ______________________________________                                    

Index 1,3,5,7 and 9 mean the intermediate degree between 0 and 2,2 and 4,4 and 6,6 and 8,8 and 10 respectively. ##EQU1##

The results are shown in Table 4.

                  TABLE 4                                                          ______________________________________                                                Degree of Damage (Index)                                                         Henry                        rice                                     Compound carb-   giant   velvet-                                                                              redroot                                                                               flat-                                    No.      grass   foxtail leaf  pigweed                                                                               sedge corn                               ______________________________________                                           I-10   10      10      10    10     10    3                                    I-20   10      10      10    10     10    0                                    I-21   10      10      10    10     10    0                                    I-35   10      10      10    10     10    0                                    I-36   10      10      10    10     10    0                                    I-48   10      10      10    10     10    1                                    I-49   10      10      10    10     10    0                                    I-50   10      10      10    10     10    0                                    I-54   10      10      10    10     10    0                                    I-55   10      10      10    10     10    1                                    I-56   10      10      10    10     10    0                                    I-57   10      10      10    10     10    0                                    I-65   10      10      10    10     10    1                                    I-81   10      10      10    10     10    0                                    I-85   10      10      10    10     10    1                                    I-97   10      10      10    10     10    2                                    I-98   10      10      10    10     10    2                                    I-99   10      10      10    10     10    0                                    I-100  10      10      10    10     10    0                                    I-101  10      10      10    10     10    3                                    I-109  10      10      10    10     10    0                                    I-133  10      10      10    10     10    0                                    I-143  10      10      10    10     10    0                                    I-I44  10      10      10    10     10    1                                    I-145  10      10      10    10     10    0                                    I-146  10      10      10    10     10    0                                    I-168  10      10      10    10     10    0                                    I-169  10      10      10    10     10    0                                    I-170  10      10      10    10     10    2                                    I-172  10      10      10    10     10    0                                    I-173  10      10      10    10     10    2                                    I-176  10      10      10    10     10    0                                    I-177  10      10      10    10     10    0                                    I-178  10      10      10    10     10    0                                    I-179  10      10      10    10     10    3                                    I-180  10      10      10    10     10    2                                    I-181  10      10      10    10     10    3                                    I-183  10      10      10    10     10    3                                    I-184  10      10      10    10     10    3                                    I-185  10      10      10    10     10    0                                    I-186  10      10      10    10     10    0                                    I-187  10      10      10    10     10    2                                    I-188  10      10      10    10     10    3                                    I-189  10      10      10    10     10    0                                    I-190  10      10      10    10     10    2                                    I-191  10      10      10    10     10    0                                    I-192  10      10      10    10     10    0                                    I-193  10      10      10    10     10    0                                    I-195  10      10      10    10     10    0                                    I-196  10      10      10    10     10    0                                    I-197  10      10      10    10     10    3                                    I-198  10      10      10    10     10    0                                    I-200  10      10      10    10     10    0                                    I-201  10      10      10    10     10    0                                    I-202  10      10      10    10     10    0                                    I-203  10      10      10    10     10    0                                    I-204  10      10      10    10     10    1                                    I-205  10      10      10    10     10    1                                    I-207  10      10      10    10     10    2                                    I-208  10      10      10    10     10    0                                    I-209  10      10      10    10     10    0                                    I-210  10      10      10    10     10    2                                    I-211  10      10      10    10     10    0                                    I-212  10      10      10    10     10    2                                    I-214  10      10      10    10     10    0                                    I-215  10      10      10    10     10    3                                    I-216  10      10      10    10     10    0                                    I-217  10      10      10    10     10    0                                    I-218  10      10      10    10     10    0                                    I-219  10      10      10    10     10    0                                    I-220  10      10      10    10     10    0                                    I-222  10      10      10    10     10    0                                    I-224  10      10      10    10     10    3                                    I-225  10      10      10    10     10    3                                    I-228  10      10      10    10     10    0                                    I-229  10      10      10    10     10    0                                    I-230  10      10      10    10     10    0                                    I-231  10      10      10    10     10    0                                    I-232  10      10      10    10     10    0                                    I-233  10      10      10    10     10    0                                    I-234  10      10      10    10     10    0                                    I-237  10      10      10    10     10    3                                    I-238  10      10      10    10     10    0                                    I-240  10      10      10    10     10    0                                    I-241  10      10      10    10     10    0                                    I-244  10      10      10    10     10    2                                    I-245  10      10      10    10     10    2                                    I-249  10      10      10    10     10    3                                    I-250  10      10      10    10     10    0                                    I-251  10      10      10    10     10    0                                    I-254  10      10      10    10     10    0                                  II-102   10      10      10    10     10    3                                  II-109   10      10      10    10     10    0                                  II-130   10      10      10    10     10    0                                  II-137   10      10      10    10     10    0                                  II-277   10      10      10    10     10    3                                  Comparative                                                                              6       7       8     4      5    7                                  Compound A                                                                     Comparative                                                                              6       5       8     2      8    6                                  Compound B                                                                     ______________________________________                                     

We claim:
 1. A compound or an optical isomer or salt thereof represented by the formula I: ##STR11## ##STR12## wherein, R¹ is (a) C₁₋₅ alkyl;(b) phenyl optionally substituted with(i) halogen, (ii) C₁₋₆ alkoxy (iii) C₁₋₄ alkyl, (iv) C₁₋₄ haloalkye, (v) C₁₋₄ alkylsulfonyl, (vi) C₁₋₄ alkoxy-C₁₋₄ alkyl, (vii) C₁₋₄ alkylthio-C₁₋₄ alkylthio, (viii) C₁₋₄ alkylthio, (ix) C₁₋₄ alkoxy-C₁₋₄ alkylthio, (x) nitro, (xi) C₁₋₄ alkylcarbonylamino, (xii) C₁₋₄ alkylthio-C₁₋₄ alkoxy, (xiii) C₂₋₄ alkenyloxy, (xiv) C₂₋₄ alkynyloxy, (xv) C₁₋₄ haloalkoxy, (xvi) C₁₋₄ dialkylaminosulfonyl, (xvii) C₂₋₄ alkenylthio, (xviii) C₁₋₄ haloalkylsulfonyl, (xix) C₂₋₄ haloalkenyloxy, (xx) C₁₋₄ alkylcarbonyl, (xxi) C₁₋₄ alkoxy-C₁₋₄ alkylsulfonyl, (xxii) C₁₋₄ alkoxy-C₁₋₄ alkoxy, (xxiii) hydroxy, (xxiv) halophenoxy, or, (xxv) benzyloxy, (c) benzyl group optionally substituted with halogen; or, (d) pyridyl group optionally substituted with(i) C₁₋₄ alkyl, (ii) halogen, or (iii) C₁₋₄ alkylsulfonyl, R² is (a) halogen,(b) C₁₋₄ alkoxy, (c) C₁₋₄ alkylthio, (d) C₁₋₄ alkylsulfonyl, (e) C₁₋₄ alkyl, (f) C₁₋₄ alkoxyalkyl, or, (g) C₁₋₄ alkoxylcarbonyl; n is an integer from 0 to 4; and, R³ and R⁴ may be the same or different and each is(a) hydrogen, or, (b) C₁₋₃ alkyl.
 2. A herbicidal composition comprising a herbicidally effective amount of a compound according to claim
 1. 3. A method of controlling weed pests and protecting corn plants which comprises adding to the habitat thereof an herbicidally effective amount of the composition according to claim 2 in a herbicidally acceptable carrier.
 4. The compound 3-(2-nitro-4-chlorobenzoyl) bicyclo heptane-2,4-dione.
 5. The compound 3-(2-chloro-4-methylsulfonyl-3-methoxybenzoyl)-cis-5-methyl-cis-bicyclo -heptane-2,4-dione.
 6. A herbicidal composition comprising a herbicidally effective amount of the compound of claim 4 and a herbicidally acceptable carrier.
 7. A herbicidal composition comprising a herbicidally effective amount of the compound of claim 5 and a herbicidally acceptable carrier. 